CN116656352A - Eutectic solvent and preparation method and application thereof - Google Patents

Eutectic solvent and preparation method and application thereof Download PDF

Info

Publication number
CN116656352A
CN116656352A CN202310648960.8A CN202310648960A CN116656352A CN 116656352 A CN116656352 A CN 116656352A CN 202310648960 A CN202310648960 A CN 202310648960A CN 116656352 A CN116656352 A CN 116656352A
Authority
CN
China
Prior art keywords
carbon quantum
quantum dot
eutectic solvent
polymer
polyethylene terephthalate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202310648960.8A
Other languages
Chinese (zh)
Other versions
CN116656352B (en
Inventor
任红威
贾本真
张金锋
赵腾达
韩亮
张秋雅
曹鹏飞
王蕾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Science and Technology
Original Assignee
Hebei University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Science and Technology filed Critical Hebei University of Science and Technology
Priority to CN202310648960.8A priority Critical patent/CN116656352B/en
Publication of CN116656352A publication Critical patent/CN116656352A/en
Application granted granted Critical
Publication of CN116656352B publication Critical patent/CN116656352B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The application relates to the technical field of flame-retardant materials, and particularly discloses a eutectic solvent and a preparation method and application thereof. The eutectic solvent is prepared from indole derivatives and phytic acid compounds in a molar ratio of 1:1-8:1; the indole derivative is at least one of 2, 3-indoline, 2-methylindole, 3-indoleacetamide, 7-azaindole, 5-cyanoindole or 3-methyloxindole; the phytic acid compound is at least one of phytic acid or phytate. And preparing the carbon quantum dots by using the eutectic solvent as a precursor through solvent reaction, and compounding the carbon quantum dots with lignosulfonate to prepare the carbon quantum dot/lignin composite material. The carbon quantum dot/lignin compound is adopted to modify the polymer, so that the flame retardant effect of the polymer can be obviously improved, the application field of the polymer is enlarged, the raw material sources are wide, the preparation process is simple, the method is suitable for large-scale production and application, and the method has wide application prospect in the flame retardant field.

Description

Eutectic solvent and preparation method and application thereof
Technical Field
The application relates to the technical field of flame-retardant materials, in particular to a eutectic solvent and a preparation method and application thereof.
Background
With the continuous development of chemical technology, the application field of the polymer is more and more extensive. However, the high molecular polymer is easy to burn, most of the polymer can be spontaneously combusted under the atmospheric condition, the limit oxygen combustion index is generally less than or equal to 21 percent, and each square meter of material is combusted to release higher energy, so that the fire is easy to continue, and the application of the high molecular polymer in the fields of electronics and electric industries, building materials and the like is greatly limited. And the combustion of the high polymer also releases toxic gas, which affects the ecological environment and human health. Therefore, development of flame retardant polymers has attracted considerable attention.
Currently, the most commonly used flame retardant modifications of polymers are mainly the addition of various flame retardants to the polymer, with the use of halogenated organic compounds and organic phosphates being most common. After the flame retardant effect of the halogen flame retardant, strong cancerogenic substances and corrosive gases are easily generated in the combustion process, so that the halogen flame retardant not only pollutes the environment, but also can harm the health of human beings, and has poor environmental protection and safety. The organic phosphate flame retardant has the defects of low flame retardant efficiency and great damage to the mechanical property and the mechanical property of the material. Therefore, the development of a novel flame-retardant polymer with environmental protection and excellent flame retardant property has very important significance for expanding the application field of the polymer.
Disclosure of Invention
Aiming at the problems of poor flame retardant property, large addition amount, poor safety, poor environmental protection and the like of the flame retardant polymer in the prior art, the application provides a eutectic solvent and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the application is as follows:
in a first aspect, the application provides a eutectic solvent which is prepared from indole derivatives and phytic acid compounds in a molar ratio of 1:1-8:1; wherein the indole derivative is at least one of 2, 3-indoline, 2-methylindole, 3-indoleacetamide, 7-azaindole, 5-cyanoindole or 3-methyloxindole; the phytic acid compound is at least one of phytic acid, sodium phytate, copper phytate or calcium phytate.
Preferably, the preparation method of the eutectic solvent comprises the following steps: and uniformly mixing the indole derivative and the phytic acid compound, heating to 40-100 ℃, and keeping the temperature until the system is uniform and transparent, thus obtaining the eutectic solvent.
The eutectic solvent in the application takes indole derivatives as hydrogen bond donors and phytic acid compounds as hydrogen bond acceptors, wherein phosphate groups in the hydrogen bond acceptors interact with secondary amine groups or other groups in the hydrogen bond donors in a hydrogen bond mode to obtain the eutectic solvent, and the prepared eutectic solvent has good chemical stability.
In a second aspect, the application provides an application of the eutectic solvent in preparing carbon quantum dots.
In a third aspect, the application also provides a preparation method of the carbon quantum dots, which comprises the following steps: adding the eutectic solvent into absolute ethyl alcohol, reacting for 10-14 h at 180-230 ℃, and carrying out solid-liquid separation to obtain the carbon quantum dot solution.
Preferably, the mass-volume ratio of the eutectic solvent to the absolute ethyl alcohol is 1:20-35, wherein the mass unit is gram and the volume unit is milliliter.
For example, the solid-liquid separation is carried out by centrifuging at a rotational speed of 8000r/min to 120000r/min, and then filtering with 0.22 μm organic filter membrane.
Indole derivatives are used as hydrogen bond donors, eutectic solvents with good chemical stability, which are obtained by taking phytic acid compounds as hydrogen bond acceptors, are used as raw materials, and the nitrogen-containing carbon quantum dots are prepared through solvothermal reaction. The carbon quantum dots prepared by the method have uniform particle size, good dispersibility and stable performance, are beneficial to expanding the application field of the carbon quantum dots, and the preparation method of the carbon quantum dots is simple and feasible, wide in raw material source, environment-friendly in preparation process and suitable for large-scale production and application.
In a fourth aspect, the application provides a carbon quantum dot, which is prepared by the preparation method of the carbon quantum dot.
Compared with the prior art, the carbon quantum dot provided by the application uses the eutectic solvent prepared from the indole derivative and the phytic acid compound as a precursor, and can be used for effectively modifying the functional group on the surface of the carbon quantum dot.
In a fifth aspect, the present application also provides a carbon quantum dot/lignin composite material, comprising the above carbon quantum dot and lignin sulfonate.
the-OH group on the surface of the carbon quantum dot can be subjected to hydrogen bonding with the sulfonic acid group in the lignosulfonate, so that the content of the carbon quantum dot in the composite material is improved, and the stability of the carbon quantum dot/lignin composite material is also improved.
Illustratively, the lignosulfonate is at least one of sodium lignosulfonate or calcium lignosulfonate.
In a sixth aspect, the present application also provides a method for preparing the carbon quantum dot/lignin composite material, which includes the following steps:
and uniformly mixing the lignosulfonate and the carbon quantum dots, heating to 60-100 ℃, carrying out heat preservation reaction for 3-5 h, carrying out solid-liquid separation, and drying to obtain the carbon quantum dot/lignin composite material.
Preferably, the mass ratio of the lignosulfonate to the carbon quantum dots is 1:1-1:10.
In a seventh aspect, the application also provides an application of the carbon quantum dot/lignin composite material in the flame-retardant field.
The carbon quantum dot/lignin composite material provided by the application contains a large number of amino groups, phosphate groups, aromatic rings, nitrogen-containing heterocycle, methoxy groups and other functional groups, the flame retardant effect of the polymer is obviously improved through nitrogen and phosphorus synergistic flame retardance, meanwhile, the thermal stability of the polymer can be improved due to the existence of the nitrogen-containing heterocycle, the aromatic rings and other groups, and the amino groups and other groups can release non-combustible gases such as ammonia gas and dilute the oxygen content of a combustion zone when being heated; in addition, when a fire disaster occurs, the base material is more easily formed into stable, compact and uniform carbide to cover the surface when being degraded, heat insulation, oxygen and other volatile gases are isolated, and the fire disaster is further restrained from spreading.
In an eighth aspect, the present application also provides a flame retardant polymer comprising a polymer substrate and the carbon quantum dot/lignin composite material described above.
The carbon quantum dot surface provided by the application is modified with the amino, phosphate ester groups, carboxyl, hydroxyl and other functional groups, so that the compatibility of the carbon quantum dot and a polymer substrate can be improved, the carbon quantum dot is easy to generate certain combination with the polymer substrate, the carbon quantum dot is not only beneficial to being uniformly distributed in the polymer substrate, but also the combination strength of the carbon quantum dot and the polymer substrate can be enhanced, the problem that the carbon quantum dot is easy to fall off during use is avoided, and the flame retardant property of the polymer is obviously enhanced.
Illustratively, the polymeric substrate is polyethylene terephthalate.
In a ninth aspect, the present application also provides a method for preparing a flame retardant polymer, comprising the steps of:
s1, adding a polymer substrate into a strong alkali solution, dipping and drying to obtain a pretreated polymer;
s2, adding the carbon quantum dot/lignin composite material into water, and uniformly mixing to obtain a modified solution;
s3, adding the pretreated polymer into a modification solution, dipping and drying to obtain a primary modified polymer;
s4, repeating the dipping step of the primary modified polymer in the step S3 for 2-5 times to obtain the flame-retardant polymer.
The preparation method of the preferable flame-retardant polymer is simple to operate, the content of the carbon quantum dot/lignin composite material in the flame-retardant polymer can be regulated and controlled, and the prepared flame-retardant polymer has excellent flame retardant property, does not contain halogen, does not generate toxic and corrosive gas during combustion, reduces harm to environment and human body, and is environment-friendly.
Preferably, in combination with the above, in S1, the strong alkali solution is sodium hydroxide solution with a concentration of 4mol/L to 5 mol/L.
Preferably, in combination with the above, in S1, the impregnation temperature is room temperature and the impregnation time is 10min to 90min.
Preferably, in combination with the above, in S2, the concentration of the carbon quantum dot/lignin composite material in the modified solution is 1wt% to 10wt%.
Preferably, in combination with the above, the mass to volume ratio of the polymer substrate to the modifying solution is 1:20 to 1:60, wherein the unit of mass is gram and the unit of volume is milliliter.
According to the application, the carbon quantum dot/lignin compound is adopted to modify the polymer, so that the flame retardant effect of the polymer is obviously improved, the application field of the polymer is enlarged, the raw material sources are wide, the preparation process is simple, the method is suitable for large-scale production and application, and the method has a wide application prospect in the flame retardant field.
Drawings
FIG. 1 is a transmission electron microscope image of the carbon quantum dots prepared in example 1 of the present application;
FIG. 2 is a transmission electron microscope image of the carbon quantum dot/lignin composite material prepared in example 1 of the present application;
FIG. 3 is a thermogravimetric view of flame retardant polyethylene terephthalate prepared in example 1 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In order to better illustrate the present application, the following examples are provided for further illustration.
Example 1
The embodiment of the application provides a eutectic solvent which is prepared from 7-azaindole and phytic acid in a molar ratio of 6:1, and specifically comprises the following steps:
uniformly mixing 5.72g (0.048 mol) of 7-azaindole and 5.32g (0.008 mol) of phytic acid, heating to 90 ℃, stirring at constant temperature for 60min, and uniformly and transparently obtaining the 7-azaindole/phytic acid eutectic solvent.
The preparation method of the carbon quantum dots by adopting the eutectic solvent specifically comprises the following steps:
1g of the prepared 7-azaindole/phytic acid eutectic solvent is taken and added into 30mL of absolute ethyl alcohol, the mixture is heated to 220 ℃ for reaction for 10h, and then the reaction solution is centrifuged for 10min at 10000rpm, and filtered by a 0.22 mu m filter membrane, thus obtaining the carbon quantum dot solution.
The preparation method of the carbon quantum dot/lignin composite material comprises the following steps:
and (3) putting 10g of sodium lignin sulfonate and 10g of the prepared carbon quantum dot solution into a three-neck flask, carrying out oil bath reaction for 4 hours at 80 ℃, filtering, and drying to obtain the carbon quantum dot/lignin composite material.
The preparation method of the flame-retardant polyethylene terephthalate comprises the following steps:
5g of polyethylene terephthalate with the thickness of 0.05mm is taken and added into 250mL of 4mol/L sodium hydroxide solution, immersed for 60min, washed to be neutral, and dried to obtain pretreated polyethylene terephthalate;
adding 5g of the prepared carbon quantum dot/lignin composite material into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, soaking the pretreated polyethylene terephthalate in the solution with the ratio of feed liquid to 1g to 40mL at room temperature for 40min, drying, and repeating soaking for 2 times to obtain the flame-retardant polyethylene terephthalate.
The pretreated polyethylene terephthalate and the prepared flame-retardant polyethylene terephthalate are respectively weighed to obtain the mass of the carbon quantum dot/lignin composite material doped in the polyethylene terephthalate, which is 0.91g.
As shown in a Transmission Electron Microscope (TEM) diagram of the prepared carbon quantum dots as shown in FIG. 1, the number of the carbon quantum dots is very rich, the particle size is uniform, and the distribution is uniform.
TEM images of the carbon quantum dot/lignin composite material prepared in this example are shown in FIG. 2. From the graph, the carbon quantum dots are uniformly distributed on the lignin, and have good dispersibility.
The limiting oxygen index of the flame-retardant polyethylene terephthalate prepared in the example is measured to be 33.8% by a limiting oxygen index measuring instrument, and the flame-retardant grade is achieved. Vertical combustion reaches UL-94V-1 grade. The residual carbon content was 20% by thermogravimetric analysis, and the initial decomposition temperature (T 5％ ) At 394℃and a maximum decomposition temperature (T) max ) At 437 c, as shown in figure 3, the highest decomposition temperature was significantly increased compared to 389.63 c for pure polyethylene terephthalate. The maximum heat release rate was 295.7W/g and the total heat release was 17.3KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 61% and the total heat release was reduced by 58% compared to pure polyethylene terephthalate.
Example 2
The embodiment of the application provides a eutectic solvent which is prepared from 2, 3-indoline and sodium phytate in a molar ratio of 5:1, and specifically comprises the following steps:
3.57g (0.03 mol) of 2, 3-indoline and 5.54g (0.006 mol) of sodium phytate (molecular weight 923.82) are uniformly mixed, heated to 100 ℃, stirred at constant temperature for 60min, and the system is uniform and transparent, thus obtaining the 2, 3-indoline/sodium phytate eutectic solvent.
The preparation method of the carbon quantum dots by adopting the eutectic solvent specifically comprises the following steps:
1g of the prepared 2, 3-indoline/sodium phytate eutectic solvent is taken and added into 20mL of absolute ethyl alcohol, the mixture is heated to 180 ℃ for reaction for 14h, and then the reaction solution is centrifuged for 10min at 12000rpm, and filtered by a 0.22 mu m filter membrane, thus obtaining the carbon quantum dot solution.
The preparation method of the carbon quantum dot/lignin composite material comprises the following steps:
and (3) putting 10g of sodium lignin sulfonate and 50g of the prepared carbon quantum dot solution into a three-neck flask, carrying out oil bath reaction for 5 hours at 60 ℃, filtering, and drying to obtain the carbon quantum dot/lignin composite material.
The preparation method of the flame-retardant polyethylene terephthalate comprises the following steps:
5g of polyethylene terephthalate with the thickness of 0.05mm is taken and added into 200mL of 5mol/L sodium hydroxide solution, immersed for 50min, washed to be neutral, and dried to obtain pretreated polyethylene terephthalate;
adding 10g of the prepared carbon quantum dot/lignin composite material into 100mL of water to obtain a modified solution; and adding the pretreated polyethylene terephthalate into the modified solution, dipping the modified solution for 10 minutes at room temperature according to the feed liquid ratio of 1g to 20mL, drying, and repeatedly dipping for 3 times to obtain the flame-retardant polyethylene terephthalate.
The pretreated polyethylene terephthalate and the prepared flame-retardant polyethylene terephthalate are respectively weighed to obtain the mass of the carbon quantum dot/lignin composite material doped in the polyethylene terephthalate, which is 0.54g.
The limiting oxygen index of the flame-retardant polyethylene terephthalate prepared in the embodiment is 31.1% by a limiting oxygen index tester, so that the flame-retardant polyethylene terephthalate reaches the flame-retardant grade. Vertical combustion reaches UL-94V-2 grade. The residual carbon content was found to be 13% by thermogravimetric analysis, the initial decomposition temperature (T 5％ ) At 392℃and a maximum decomposition temperature (T) max ) Is 432 ℃. The maximum heat release rate was 392.5W/g and the total heat release was 21.9KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 49% compared to pure polyethylene terephthalate, total heat releaseThe drop is 47 percent.
Example 3
The embodiment of the application provides a eutectic solvent which is prepared from 3-indoleacetamide and copper phytate in a molar ratio of 3:1, and specifically comprises the following steps:
6.80g (0.039 mol) of 3-indoleacetamide and 13.38g (0.013 mol) of copper phytate are uniformly mixed, heated to 40 ℃, stirred at constant temperature for 120min, and the system is uniform and transparent, thus obtaining the 3-indoleacetamide/copper phytate eutectic solvent.
The preparation method of the carbon quantum dots by adopting the eutectic solvent specifically comprises the following steps:
1g of the prepared 3-indoleacetamide/copper phytate eutectic solvent is taken and added into 25mL of absolute ethyl alcohol, the mixture is heated to 230 ℃ for reaction for 10 hours, and then the reaction solution is centrifuged for 10 minutes at 9000rpm and filtered by a 0.22 mu m filter membrane, thus obtaining the carbon quantum dot solution.
The preparation method of the carbon quantum dot/lignin composite material comprises the following steps:
10g of calcium lignosulfonate and 40g of the prepared carbon quantum dot solution are placed into a three-neck flask, oil bath reaction is carried out at 100 ℃ for 3 hours, filtration is carried out, and drying is carried out, thus obtaining the carbon quantum dot/lignin composite material.
The preparation method of the flame-retardant polyethylene terephthalate comprises the following steps:
5g of polyethylene terephthalate with the thickness of 0.05mm is taken and added into 230mL of 4.5mol/L sodium hydroxide solution, immersed for 90min, washed with water to be neutral, and dried to obtain pretreated polyethylene terephthalate;
adding 1g of the prepared carbon quantum dot/lignin composite material into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, dipping the modified solution for 90 minutes at room temperature according to the feed liquid ratio of 1g to 60mL, drying, and repeatedly dipping the modified solution for 2 times to obtain the flame-retardant polyethylene terephthalate.
The pretreated polyethylene terephthalate and the prepared flame-retardant polyethylene terephthalate are respectively weighed to obtain the mass of the carbon quantum dot/lignin composite material doped in the polyethylene terephthalate, which is 0.32g.
The limiting oxygen index of the flame-retardant polyethylene terephthalate prepared in the embodiment is measured to be 32.3% by a limiting oxygen index measuring instrument, so that the flame-retardant grade is achieved. Vertical combustion reaches UL-94V-1 grade. The residual carbon content was 17% by thermogravimetric analysis, the initial decomposition temperature (T 5％ ) At 387℃and a maximum decomposition temperature (T max ) Is 427 ℃. The maximum heat release rate was 374W/g and the total heat release was 19.7KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 51% and the total heat release was reduced by 52% compared to the pure polyethylene terephthalate.
Example 4
The embodiment of the application provides a eutectic solvent which is prepared from 2-methylindole and phytic acid in a molar ratio of 8:1, and specifically comprises the following steps:
7.36g (0.056 mol) of 2-methylindole and 4.62g (0.007 mol) of phytic acid are uniformly mixed, heated to 60 ℃, stirred at constant temperature for 90min, and the system is uniform and transparent, thus obtaining the 2-methylindole/phytic acid eutectic solvent.
The preparation method of the carbon quantum dots by adopting the eutectic solvent specifically comprises the following steps:
1g of the prepared 2-methylindole/phytic acid eutectic solvent is taken and added into 35mL of absolute ethyl alcohol, the mixture is heated to 200 ℃ for reaction for 12h, and then the reaction solution is centrifuged for 10min at 8000rpm and filtered by a 0.22 mu m filter membrane, thus obtaining the carbon quantum dot solution.
The preparation method of the carbon quantum dot/lignin composite material comprises the following steps:
10g of calcium lignosulfonate and 100g of the prepared carbon quantum dot solution are placed into a three-neck flask for oil bath reaction at 70 ℃ for 4 hours, and then the carbon quantum dot/lignin composite material is obtained after filtration and drying.
The preparation method of the flame-retardant polyethylene terephthalate comprises the following steps:
5g of polyethylene terephthalate with the thickness of 0.05mm is taken and added into 240mL of 4mol/L sodium hydroxide solution, immersed for 40min, washed to be neutral, and dried to obtain pretreated polyethylene terephthalate;
adding 3g of the prepared carbon quantum dot/lignin composite material into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, dipping the modified solution for 60 minutes at room temperature according to the feed liquid ratio of 1g to 50mL, drying, and repeatedly dipping the modified solution for 3 times to obtain the flame-retardant polyethylene terephthalate.
The pretreated polyethylene terephthalate and the prepared flame-retardant polyethylene terephthalate are respectively weighed to obtain the mass of the carbon quantum dot/lignin composite material doped in the polyethylene terephthalate, which is 0.71g.
The limiting oxygen index of the flame-retardant polyethylene terephthalate prepared in the embodiment is measured to be 30.6% by a limiting oxygen index measuring instrument, so that the flame-retardant grade is achieved. Vertical combustion reaches UL-94V-1 grade. The flame retardant polyethylene terephthalate prepared in this example was subjected to thermogravimetric analysis to obtain a carbon residue of 18% and an initial decomposition temperature (T 5％ ) At 391℃and a maximum decomposition temperature (T) max ) Is 432 ℃. The maximum heat release rate was 423W/g and the total heat release was 22.4KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 45% and the total heat release was reduced by 46% compared to the pure polyethylene terephthalate.
Example 5
The embodiment of the application provides a eutectic solvent which is prepared from 3-methyl hydroxy indole and calcium phytate in a molar ratio of 1:1, and specifically comprises the following steps:
1.912g (0.013 mol) of 3-methyl oxindole and 9.37g (0.013 mol) of calcium phytate (molecular weight 720.399) are uniformly mixed, heated to 90 ℃, stirred at constant temperature for 60min, and the system is uniform and transparent, thus obtaining the 3-methyl oxindole/calcium phytate eutectic solvent.
The preparation method of the carbon quantum dots by adopting the eutectic solvent specifically comprises the following steps:
1g of the prepared 3-methyl hydroxy indole/calcium phytate eutectic solvent is taken and added into 30mL of absolute ethyl alcohol, the mixture is heated to 190 ℃ for reaction for 13h, and then the reaction solution is centrifuged for 10min at 10000rpm, and filtered by a 0.22 mu m filter membrane, thus obtaining the carbon quantum dot solution.
The preparation method of the carbon quantum dot/lignin composite material comprises the following steps:
and (3) putting 10g of sodium lignin sulfonate and 60g of the prepared carbon quantum dot solution into a three-neck flask, carrying out oil bath reaction for 3 hours at 90 ℃, filtering, and drying to obtain the carbon quantum dot/lignin composite material.
The preparation method of the flame-retardant polyethylene terephthalate comprises the following steps:
5g of polyethylene terephthalate with the thickness of 0.05mm is taken and added into 250mL of 5mol/L sodium hydroxide solution, immersed for 10min, washed to be neutral, and dried to obtain pretreated polyethylene terephthalate;
adding 7g of the prepared carbon quantum dot/lignin composite material into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, soaking the pretreated polyethylene terephthalate in the solution with the ratio of 1g to 30mL at room temperature for 30min, drying, and repeating soaking for 4 times to obtain the flame-retardant polyethylene terephthalate.
The pretreated polyethylene terephthalate and the prepared flame-retardant polyethylene terephthalate are respectively weighed to obtain the mass of the carbon quantum dot/lignin composite material doped in the polyethylene terephthalate, which is 0.92g.
The limiting oxygen index of the flame-retardant polyethylene terephthalate prepared in the example is 29.7% by a limiting oxygen index tester, so that the flame-retardant grade is achieved. Vertical combustion reaches UL-94V-2 grade. The residual carbon content was 16% by thermogravimetric analysis, the initial decomposition temperature (T 5％ ) At 389℃and a maximum decomposition temperature (T max ) Is 430 ℃. The maximum heat release rate was 402.4W/g and the total heat release was 20.9KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 48% and the total heat release was reduced by 49% compared to pure polyethylene terephthalate.
Comparative example 1
The comparative example provides a flame retardant polyethylene terephthalate, the preparation method of which comprises the following steps:
step a, preparing a carbon quantum dot solution according to the same steps as those of the embodiment 1;
step b, adding 5g of polyethylene terephthalate with the thickness of 0.05mm into 250mL of 4mol/L sodium hydroxide solution, soaking for 60min, washing with water to be neutral, and drying to obtain pretreated polyethylene terephthalate;
step c, adding 5g of the prepared carbon quantum dot solution into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, soaking the pretreated polyethylene terephthalate in the solution with the ratio of feed liquid to 1g to 40mL at room temperature for 40min, drying, and repeating soaking for 2 times to obtain the flame-retardant polyethylene terephthalate.
The flame retardant polyethylene terephthalate prepared in this comparative example was measured to have a limiting oxygen index of 26% by a limiting oxygen index meter, and was a flammability grade. The flame retardant polyethylene terephthalate prepared in this example was subjected to thermogravimetric analysis to obtain a carbon residue having a residual ratio of 14% and an initial decomposition temperature (T 5％ ) At 382℃and a maximum decomposition temperature (T) max ) Was 423 ℃. The maximum heat release rate was 654.6W/g and the total heat release was 34.52KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The maximum heat release rate was reduced by 15% and the total heat release was reduced by 17% compared to pure polyethylene terephthalate.
Comparative example 2
The comparative example provides a flame retardant polyethylene terephthalate, the preparation method of which comprises the following steps:
step a, adding 5g of polyethylene terephthalate with the thickness of 0.05mm into 250mL of 4mol/L sodium hydroxide solution, soaking for 60min, washing with water to be neutral, and drying to obtain pretreated polyethylene terephthalate;
step b, adding 5g of sodium lignin sulfonate into 100mL of water to obtain a modified solution; adding the pretreated polyethylene terephthalate into the modified solution, dipping the modified solution for 40 minutes at room temperature according to the feed liquid ratio of 7g to 40mL, drying, and repeatedly dipping the modified solution for 2 times to obtain the flame-retardant polyethylene terephthalate.
The flame retardant polyethylene terephthalate prepared in this comparative example was found to have a limiting oxygen index of 25.7% by a limiting oxygen index meter, which is a flammable grade. The flame retardant polyethylene terephthalate prepared in this example was subjected to thermogravimetric analysis to obtain a carbon residue remaining ratio of 11% and an initial decomposition temperature (T 5％ ) At 383℃and a maximum decomposition temperature (T max ) Is 424 ℃. The maximum heat release rate was 724.1W/g and the total heat release was 37.4KJ/m as measured by micro-calorimetric analysis 2 . The maximum heat release rate of the pure polyethylene terephthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 24% and the total heat release was reduced by 10% compared to pure polyethylene terephthalate.
Comparative example 3
3.57g of 2, 3-indoline and 0.53g of glycerol are mixed, added into a 250mL three-mouth bottle, transferred into an oil bath pot at 90 ℃ and magnetically stirred for reaction for 2 hours, so that a uniform transparent solution is not obtained, and even if the temperature is raised to 120 ℃ and the reaction time is prolonged to 4 hours, the uniform transparent liquid is not obtained, namely the same eutectic solvent is not obtained.
Comparative example 4
This comparative example provides a flame retardant polyethylene terephthalate prepared in exactly the same manner as in example 1, except that the phytic acid was replaced with an equal proportion of glycerol, i.e. the phytic acid was replaced with an equal molar amount of glycerol, and the remainder was exactly the same.
The flame retardant polyethylene terephthalate prepared in this example was found to have a limiting oxygen index of 23.4% by a limiting oxygen index meter, which is a flammable grade. The flame retardant polyethylene terephthalate prepared in this example was subjected to thermogravimetric analysis to give a carbon residue of 16% and an initial decomposition temperature (T 5％ ) At 492℃and a maximum decomposition temperature (T) max ) Is 523 ℃. The maximum heat release rate was 569.9W/g and the total heat release was 33.7KJ/m as determined by micro-calorimetric analysis 2 . Pure poly-pairThe maximum heat release rate of the ethylene glycol phthalate is 770.1W/g, and the total heat release is 41.6KJ/m 2 . The peak heat release rate was reduced by 26% and the total heat release was reduced by 19% compared to pure polyethylene terephthalate.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the application.

Claims (10)

1. The eutectic solvent is characterized by being prepared from indole derivatives and phytic acid compounds in a molar ratio of 1:1-8:1; wherein the indole derivative is at least one of 2, 3-indoline, 2-methylindole, 3-indoleacetamide, 7-azaindole, 5-cyanoindole or 3-methyloxindole; the phytic acid compound is at least one of phytic acid, sodium phytate, copper phytate or calcium phytate.
2. The eutectic solvent of claim 1, wherein the method of preparing the eutectic solvent comprises the steps of: and uniformly mixing the indole derivative and the phytic acid compound, heating to 40-100 ℃, and keeping the temperature until the system is uniform and transparent, thus obtaining the eutectic solvent.
3. Use of the eutectic solvent according to claim 1 or 2 for the preparation of carbon quantum dots.
4. The preparation method of the carbon quantum dot is characterized by comprising the following steps of: adding the eutectic solvent of any one of claims 1-3 into absolute ethyl alcohol, reacting for 10-14 h at 180-230 ℃, and carrying out solid-liquid separation to obtain the carbon quantum dot solution.
5. The carbon quantum dot is characterized by being prepared by the preparation method of the carbon quantum dot in claim 4.
6. A carbon quantum dot/lignin composite material comprising the carbon quantum dot and lignin sulfonate of claim 5.
7. The method for preparing the carbon quantum dot/lignin composite material according to claim 6, comprising the steps of:
uniformly mixing lignin sulfonate and the carbon quantum dots according to claim 5, heating to 60-100 ℃, carrying out heat preservation reaction for 3-5 h, carrying out solid-liquid separation, and drying to obtain the carbon quantum dot/lignin composite material.
8. The use of the carbon quantum dot/lignin composite material of claim 6 in the flame retardant field.
9. A flame retardant polymer comprising a polymeric substrate and the carbon quantum dot/lignin composite of claim 6.
10. A method of preparing a flame retardant polymer according to claim 9, comprising the steps of:
s1, adding a polymer substrate into a strong alkali solution, dipping and drying to obtain a pretreated polymer;
s2, adding the carbon quantum dot/lignin composite material in claim 6 into water, and uniformly mixing to obtain a modified solution;
s3, adding the pretreated polymer into a modification solution, dipping and drying to obtain a primary modified polymer;
s4, repeating the dipping step of the primary modified polymer in the step S3 for 2-5 times to obtain the flame-retardant polymer.
CN202310648960.8A 2023-06-02 2023-06-02 Eutectic solvent and preparation method and application thereof Active CN116656352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310648960.8A CN116656352B (en) 2023-06-02 2023-06-02 Eutectic solvent and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310648960.8A CN116656352B (en) 2023-06-02 2023-06-02 Eutectic solvent and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN116656352A true CN116656352A (en) 2023-08-29
CN116656352B CN116656352B (en) 2024-05-10

Family

ID=87723837

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310648960.8A Active CN116656352B (en) 2023-06-02 2023-06-02 Eutectic solvent and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116656352B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892038A (en) * 2020-08-12 2020-11-06 河北科技大学 Acidic carbon quantum dot and preparation method and application thereof
CN112048334A (en) * 2020-08-31 2020-12-08 上饶师范学院 Method for extracting and denitrifying aromatic acid eutectic solvent
CN114989821A (en) * 2022-06-13 2022-09-02 河北科技大学 Eutectic solvent, fluorescent carbon quantum dot, preparation method and application
CN116036292A (en) * 2022-02-18 2023-05-02 复旦大学 Eutectic mixture with solubilization and absorption promotion effects and drug-loaded composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892038A (en) * 2020-08-12 2020-11-06 河北科技大学 Acidic carbon quantum dot and preparation method and application thereof
CN112048334A (en) * 2020-08-31 2020-12-08 上饶师范学院 Method for extracting and denitrifying aromatic acid eutectic solvent
CN116036292A (en) * 2022-02-18 2023-05-02 复旦大学 Eutectic mixture with solubilization and absorption promotion effects and drug-loaded composition
CN114989821A (en) * 2022-06-13 2022-09-02 河北科技大学 Eutectic solvent, fluorescent carbon quantum dot, preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YU CHEN等: "Efficient Recovery of Valuable Metals from Lithium-Ion Battery Cathodes Using Phytic Acid-Based Deep Eutectic Solvents at a Mild Temperature", ENERGY FUELS, vol. 37, 24 March 2023 (2023-03-24), pages 5361 *

Also Published As

Publication number Publication date
CN116656352B (en) 2024-05-10

Similar Documents

Publication Publication Date Title
Liu et al. Synthesis of a novel nonflammable eugenol-based phosphazene epoxy resin with unique burned intumescent char
CN109180952B (en) Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof
Wang et al. Synthesis of a hyperbranched polyamide charring agent and its flame-retarding and toughening behavior in epoxy resin
CN107090083A (en) It is nitrogen phosphorus siliceous copolymer of main chain and preparation method and application containing double-deck silsesquioxane
CN109161052B (en) Ternary hybrid flame retardant, flame-retardant polylactic acid material and preparation method thereof
CN107652468A (en) Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO
CN110746646B (en) Biomass-based flame retardant and preparation method thereof
CN108976418B (en) Three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene and preparation method thereof
CN114920713A (en) Flame-retardant curing agent, and preparation method and application of reactive epoxy resin
CN116656352B (en) Eutectic solvent and preparation method and application thereof
WO2021037273A1 (en) Covalent organic frame flame retardant having schiff base-containing vanillin group, and preparation method therefor
Shu et al. Preparation and properties of bio-based flame retardant polyvinyl alcohol
CN105801867B (en) A kind of expansion type flame retardant and preparation method thereof based on biomass structure
Ou et al. A High‐Efficient DOPO‐Based Flame Retardant as a Co‐Curing Agent for Simultaneously Enhancing the Fire Safety and Mechanical Properties of Epoxy Resin
CN110078715B (en) Flame-retardant high-temperature-resistant bifunctional epoxy resin containing heteronaphthalene biphenyl structure and synthesis method thereof
CN112250712A (en) DOPO-containing bisphthalonitrile flame retardant and preparation method and application method thereof
CN107501526B (en) DOPO type epoxy resin curing agent and preparation method thereof
CN109503884B (en) Tryptamine flame retardant and synthesis and application thereof
CN108485192B (en) N-P synergistic high-flame-retardant epoxy resin composition with excellent flexibility and preparation method thereof
CN107674303B (en) Modified kaolin flame-retardant synergist and preparation method and application thereof
CN114525019B (en) Preparation method and application of DOPO-GMA-APP flame retardant
CN110526943A (en) A kind of high content of phosphorus hydrolysis fire retardant and preparation method thereof
CN114685937A (en) Flame-retardant epoxy resin composite material and preparation method thereof
CN115572309A (en) Efficient flame-retardant anti-dripping environment-friendly flame retardant
CN115594943A (en) Modified carbon nanotube flame-retardant reinforced epoxy resin and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant